Omega-haloalkyl benzhydryl ether and methods of making same



Patented Sept. 11, 1951 OMEGA-HALOALKYL BENZHYDRYL ETHER AND METHODS OF MAKING SAME George RieveschLJn, Grosse Pointe Woods, Mich., assignor to Parke, Davis & Company, Detroit, Mich., a corporation of Michigan N Drawing. Application August 5, 1946, Serial No. 688,420

- Claims. (Cl. 260-611) 1. v I The invention relates to halogen ethers and t a novel method for obtaining the same. More particularly, the invention relates to w-haloalkyl' benzhydrylethers having the formula,

ono 0112),);

where R1 and R2 are the same or difierentsubstituents and represent hydrogen, a lower alkyl radical or a lower alkoxy radical, n is one of the integers two and three and X is a chlorine or bromine atom. a a

This application is a, continuation-in-part of my copending application Serial No. 531,639, filed April 18, 1944, now Patent No. 2,421,714, issued June 3, 1947.

The customary method of producing o-haloalkyl ethers consists in reacting a metal alcoholate with a halohydrin to obtain an w-hydroxyalkyl ether which is then treated with a halogenating agent such as thionyl chloride or a phosphorus halide to convertthe hydroxyl group to a halogen atom.-- This two-step method of producing w-haloalkyl others is not only tedious but unsatisfactory from the standpoint of yields. o

It is well-known that when halohydrins such as ethylene chlorohydrin are treated with cold aqueous alkali that they are rapidly hydrolyzed to the corresponding glycol. Under anhydrous conditions halohydrins react readily with alkaline reagents to produce the'corresponding alkylene oxide. In spite of the great reactivity of the halogen atom of the halohydrins in the presence of alkaline reagents, I have discovered that w-halohydrins may be heated with a mixture of an alkali metal carbonate and a benzhydryl halide of the formula.

where R1, Brand X have the same significance as given above, to produce high yields of the corresponding whaloalkyl benzhydryl others. This one-step process is preferably carried out in the absence of a solvent and at a temperature of between about 100 and 160 C. However, if de- 2 sired, an anhydrous, inert organic solvent such as toluene or xylene may be used.

An excess or the alkali metal carbonate and halohydrin are usually used in carrying out the reaction to insure the completeutilization of the more expensive benzhydryl halide. However, it should be understood that it is not necessary to use an excess of the halohydrin and that the benzhydryl halide-halohydrin mol ratio may be reversed so long as suflicient alkali metal carbonate is used to react with the hydrogen halide formed during the reaction. quantities of the three reactants can be calculated from the following equation which illustrates the transformations which take place during the process.

CHO(CH2),,X 2MX 002 -I- 11:40

Example 1. 3-Bromoethyl benzhydryl ether onocmcmm 3 A" mixture consisting of 494 g. of benzhydryl bromide, 206 g. of anhydrous sodium carbonate and 313 g. ,of ethylene bromohydrin is stirred and heated at -l30 C. for eight hours. During the reaction carbon dioxide is evolved. After cooling, 50000. of benzene is added with stirring,

The theoretical 3 the precipitate of inorganic salts filtered 011 and washed with benzene. The benzene is removed by distillation and the' residual fi-bromoethyl benzhydryl ether purified by distillation in vacuo; B. P. 169-72 C./2 mm.

Example 2.-;6-'Chloroethyl be zhydryl :ether CHO 0111011101 A mixture consisting of 474 g. of benzhydryl bromide, 120 g. of anhydrous potassium carbonate and 200 g. of ethylene chlorohydrin is heated at 130 C. with stirring .for eighthours. At the end of this time the evolution of carbon dioxide has practically ceased. The residue is cooled, stirred with 700 cc. of ether and the insoluble inorganic salts removed by filtration. The ether is distilled from .the filtrate and "the residue distilled in vacuo to obtain the .desired p-chloroethyl 'benzhydryl ether boiling :at 100 04/10 mm. :or "163 C./ 7 mm.; yield 80%.

Example ,3.p-Br.omoethul p,p-dimetitylbenzhydryl ether IJH'O-CHaCHaBr 331 g. of 'p,=p'-dimethylbenzhydryl chloride, 130 vof anhydrous sodium carbonate and 250 g.-o'f ethylene bromohydrin are heated with stirring at 135 C. for ten hours. The reaction mixture is cooled, treated with 500 cc. of benzene and the inorganic material which fails to dissolve in the benzene removed by filtration. The benzene is removed fromthe filtrate by distillation and the residue distilled in vacuo (c. a. at about '2 mm. pressure) to obtain the desired ,B-bromoethyl p,p-dimethylbenzhydryl ether as a colorless liquid.

Example 4.--y-Chloropropyl o-methoxybenzhydryl ether BHO'GHaEHaCH: G1

A mixture consisting of .267 g. of o-methoxybenzhydryl bromide, 120 g. of anhydrous potassium carbonate and .125 .g. of trimethylene .chlorohyfirinin 200 cc. .of xylene is heated with stirring at 135 C. for ten hours. The mixture is cooled, diluted with 200 cc. of xylene and the inorganic salts removed by filtration. The xylene is .distilled from the filtrate and the residue distilled under reduced pressure to obtain the desired 'y-chloropropyl omethoxybenzhydryl ether.

Attention is called to other somewhat related copending applications as follows: Serial No. 640,685, filed January 11, .1946, now abandoned; Serial No. 640,686, filed January 11, 1946 which issued as Patent No. 2,508,422; 'Serial No. 640,687, filed January 11, 1946, now abandoned; Serial No. 660,406, filed April 8, 1946, which issued as PatentNo. 2,483,434; Serial No. 688,421, filed August 5, 1946; Serial No. 688,422, filed August 5, 1946, now abandoned; Serial No. 688,423, filed August .5, 1946, now abandoned; Serial No. 688,-.

424, filed August 5, 1946, which issued as Patent No. 2,453,729; Serial No. 688,425, filed August 5, 1946, which issued as Patent No. 2,483,435; Serial No. 688,426, filed August 5, 1946, which issued as Patent No. 2,437,711; Serial No. 688,427, :filed August '5, 1946, which deemed as Patent No. 2 ,483,436;Seria1.No. 739,985, filed April 8, 1947, which issued as Patent No. 2,437,878; Serial No. 751,983, filed June 2, 1947, which issued as Patent .No. 2,454,092; Serial No. 751,984, filed June 2, 19.47,, -.whichiissued as'Patent No. 2,483,671; Serial No. 751,985, filed June 2, 1947, which issued as .Patent .No. 2,455,949; Serial No. 780,099, filed October 15, 1947, which issued as Patent No. "2527;962; Serial No. 15,257, filed March 16, 1948; .-and Serial No. 33,432, filed June 16, 1948, which :issuedas Patent No. 2,527,963.

What I claim as my invention is:

-1. An w-haloalkyl benzhydryl ether of the formula,

mikeom) l-x with an metal carbonate and zbenzhydryl halide of the formula.

crux at a temperature between about and I1, where R1 and R2 are members of the class consisting :of hydrogen, lower alkyl :and lower :a lkoxyl, n :is one of the integers two and three and X is 'a member of the class consisting of chlorine and bromine.

6. Process for obtaining an haloalkyl benzhydryl ether of the formula,

which comprises heating an 'w-halohydrinof the o mul HO(CH2)n-X with an alkali metal carbonate and a benzhydryl halide of the formula,

CHX

where X is a member of the class chlorine and bromine, at a temperature between about 100 to 160 C.

8. Process for obtaining c-chloroethyl benzhydryl ether which comprises heating under anhydrous conditions in the absenceof a solvent, ethylene chlorohydrin with an alkali metal carbonate and a benzhydryl halide of the formula,

where X is a member of the class consisting of chlorine and bromine, at a temperature between about 100 and 160 C.

9. Process for obtaining 'y-chloropropyl omethoxy benzhydryl ether which comprises heating under anhydrous conditions in the absence of a solvent, trimethylene chlorohydrin with an alkali metal carbonate and a benzhydryl halide of the formula,

where X is a member of the class consisting of chlorine and bromine, at a temperature of between about and C.

10. A fl-haloethyl benzhydryl ether of the formula,

CH-O-CHz CH2X where X is a member of the class consisting of chlorine and bromine.

GEORGE RIEVESCHL, JR.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,130,525 Coleman Sept. 20, 1938 2,397,799 Martin et a1 Apr. 2, 1946 OTHER REFERENCES Friedel et al.: Bulletin de la Societe Chimique de Paris, 2nd series (1880), pages 339, 340. 

1. AN W-HALOALKYL BENZHYDRYL ETHER OF THE FORMULA, 